Process of manufacturing olefins and their oxidation products.



CHARLIES J. GREENSTREET, 0F WEBSTER GROVES, MISSOURI.

PROCESS OF MANUFACTURING OLEFINS AND THEIR OXIDATION PRODUCTS.

1,110,925. No Drawing.

Specification of Letters Patent. Application filed June 7, 1912. Serial No.702,176.

Patented Sept, 15, 191%.

dation Products, of which the following is a specification.

The principal objects of my invention are to devise a practical method of manufacturing olefins from mineral oils and also to devise a practical method of manufacturing sfilcohols, aldehydes and fatty acids thererom.

The invention consists in the hereinafter described treatment of mineral oil to obtain a large proportion of olefins therefrom.

It also consists in the oxidation of olefin to obtain alcohols, aldehydes and acids therefrom. It also consists in the steps and processes hereinafter more fully described.

The liquid product resultin from the treatment "of crude oil by t e so-called cracking process is a mixture consisting almost wholly of araflins with a comparatively small uant ty of olefins. The liquid product resu ting from the treatment of crude oil by a process invented by me and described in my co-pending application Ser. No. 696,891, filed May 13, 1912, is a mixture consisting of paraflins with a considerable proportion of olefins. As more fully described in said application, my said process consists in forcing the crude oil to and through an atomizer on the inlet side of a coil of pipe of uniform diameter kept at a substantially cherry red temperature, the oil being thoroughly commingled at the atomizer with steam under a considerable pressure, say about one-hundred pounds per uare inch, the quantity of steam being that o a column of water substantially equal to or greater than the volume of the oil. In order to increase the production of olefin, the product resulting from the treatment just described is itself submitted to the same treatment; that is, the condensate resulting from the passing of the crude oil through a lon hot coil under the conditions above state is again passed through such a coil under substantiall the same conditions. In conse uence of this repeated operation, the resulting product contains a very large. percentage o olefins.

Whether the mixture of paraflins and olefins is obtained by the cracking process or by my said process, or otherwise, sulfuric acid is added thereto in suflicient quantity to convert the olefins into the corresponding sulfonlc ethers. Water is then added to convert such ethers into the corresponding alco hols. In the meanwhile, the paraflins remain unchanged. For some purposes, it may be unnecessary to separate the paraflins from the alcohols. Usually, however, it will be desirable to separate the parafiins from the alcohols; and in order-to accomplish such separation, the mixture is subjected to the process of fractional distillation. Fractional distillation 'is especially available for such separation by reason of the fact that, whereas plefins and paraflins of substantially the same specific gravity distil at nearly the same temperatures, there is a very wide difference in the distillation points of paraflins and the corresponding olefins on the one side compared with the alcohols derived therefrom on the other. Thus, while the olefin C l-I' distils at a temperature of one hundred and twenty-three degrees ccntigrade, the

corresponding alcohol C,H,,,O distils at a temperature of from one hundred and eight to one hundred and ninety degrees centlgrade.

When it is desired to convert the olefins of the mixture into the aldehydes or acids,

a strong oxidizing agent, such as chromic acidv or alkaline permanganate of potassium may be used. The result of the reaction of these last mentioned reagents upon the olefins is to convert them into alcohols, aldehydes and acids. Hypochlorous acid unites also with the olefins to form chlorhydrins which can be converted into corresponding oxids, as for instance, by heating with a solution of causti soda or other caustic alkali.

It is noted that whether-the olefins are treated with sulfuric acid or with by 0- chlorous acid or with chromic acid or aliialine permanganate of potassium, the general result in each case is an oxidation of the olefin. It is further noted that (with the exception of hypochlorous acid) all of these reagents efi'ect a direct oxidation of the olefins, that is, oxidation with a single reagent, whereas treatment with hypochlorous acid indirectly brings about oxidation, that is, treatment with hypochlorous acid produces an intermediate compound which requires an additional reagent to effect oxi-- [continuous pipe at a substantially dation thereof by substitution. These reagents react to produce diiferent specific results; and the choice of a reagent will depend to a certain extent upon the product desired. Instead of the reagents specified,

their proper chemical equivalents may be substituted therefor. For instance hydrochloric acid may be used as a substitute for sulfuric acid and constitutes an equivalent therefor, but in such case, hydrochloric ether is formed instead of sulfonic ether, and such hydrochloric ether is immediately converted into alcohols in the same manner as the sulfonic ether. Likewise, it is obvious that the presence of the paraflins is not of any.

impphrtance in the treatment of the olefins.

at I claim as my invention and desire 'to secure by Letters Patent is:

1.' The p'ocess of manufacturmg olefins 4 which consists in forcing mineral 011 commingled with steam through a long coil of heat and repeating the operation upon the result ing product. 2. The process of treating crude oil which consists in forcing it oommmgled with steam through a lon continuous coil of pipeat a substantially c err red heat, and oxidizing the olefin in 'ents of the resulting product. v 3. The process of treating crude oil which consists in forcing it commingled with steam through a long continuous coil of pipe at a substantialliyi cherry red heat, oxidizin the olefin ingl'e 'ents of the resulting pr uct, and separating the oxidation product by fractional disti ation..

Signed at St. Louis, Missouri, this 5th day. ofJune, 1912. I

CHARLES J. GREENSTREET.

Witnesses:

Amna'r H. Cnorssm'r, M. A, S am/mu. 

